Catalyst for polymerization of olefins

ABSTRACT

Catalysts for polymerization of olefin which comprise a solid catalyst component (A) and an organometallic compound with a heterocyclic carboxylic acid ester (B), wherein the solid catalyst component (A) is obtained by reacting or/and grinding an organomagnesium compound (1), of the formula 
     
         M.sub.α Mg.sub.β R.sub.p.sup.1 R.sub.q.sup.2 X.sub.r 
    
     wherein 
     α, p, q and r each independently ≧0, 
     β&gt;0, 
     p+q+r=mα+2β 
     M is Al, Zn, B or Be, 
     m is the valence of M, 
     R 1  and R 2  are the same or different hydrocarbon groups having 1-20 carbon atoms, and 
     X is a halogen atom, 
     or of the reaction product of M.sub.α Mg.sub.β R p   1  R q   2  X r  with an electron donor, with 0.01 to 100 moles of (ii) a chlorosilane compound containing Si-H bonds and of the formula 
     
         H.sub.a SiClR.sub.4-(a+b).sup.3 
    
     wherein 
     
         0&lt;a≦2, 
    
     a titanium halide (2) and a carboxylic acid ester (3); and the heterocyclic carboxylic acid ester is N--, S--, or O--containing heterocyclic compound, and processes for polymerization of olefin employing such a catalyst.

This invention relates to highly active catalysts for highlystereospecific polymerization of olefins and to polymerization processesemploying such catalysts. In particular, the present invention issuitable for polymerizing stereospecifically propylene, butene-1,3-methyl-butene-1, pentene-1, 4-methyl-pentene-1 and the like, or alsofor copolymerizing said olefin with ethylene or other olefins.

It has been well known that stereospecific polymers are produced byusing a Ziegler-Natta catalyst system comprising a transition metalcompound of a metal Groups IV to VIA of the Periodic Table and anorganometallic compound of a metal of Groups I-III of the PeriodicTable. Particularly, a combination of a titanium halide and anorganoaluminum compound such as triethylaluminum or diethylaluminumchloride is widely used in industrial production as a catalyst forstereospecific polymerization of olefins.

Polymerization of olefins such as propylene carried out with this typeof catalyst results in a relatively high stereospecifity, which is shownby a ratio of boiling heptane insoluble polymers to soluble polymers,i.e., stereospecific polymers. However, the polymerization activity ofthe catalyst is not fully satisfactory and removal of catalyst residuefrom the resultant polymer is necessary.

Recently, as highly active catalysts for olefin polymerization, manycatalysts have been proposed which comprise an inorganic- ororganomagnesium compound and a titanium or vanadium compound, or thesetwo components plus an electron donor. For example such catalysts havebeen known as those using a magnesium halide (British Pat. Nos.1,335,887, 1,387,888, 1,387,889, 1,387,890 and Japanese PatentPublication Nos. 52-36786, 52-36913), those using a magnesium alkoxide(Japanese Patent Laid Open No. 49-149193), those using a magnesiumhydroxy chloride (Canadian Pat. No. 739,550 which corresponds toJapanese Patent Publication No. 43-13050), those using a magnesiumcarbonate (Japanese Patent Publication No. 46-34094), those using amagnesium oxide (Japanese Patent Publication No. 46-11669), those usingan alkylmagnesium (British Pat. No. 1,373,981), those using Grignardcompound (British Pat. No. 1,390,001) and those wherein a titanium or avanadium compound is supported on a carrier which is produced bytreating a magnesium halide with Si(OR)_(n) X_(4-n), wherein X ishalogen, (Japanese Patent Publication No. 51-37194).

Some of these catalyst show notable activity for polymerization ofolefins but with too much amorphous content, or other of these catalystsshow high stereoregularity but with insufficiency in polymerizationactivity. Therefore, they are hardly used per se as catalyst for newindustrial stereospecific polymerization of olefins, for which it isnecessary to have both sufficient polymerization activity andstereoregularity. Particularly, they are insufficient in polymer yieldper solid catalyst component, and the polymers produced have a largecontent of halogen which brings about corrosion of polymerizationequipment and molding machines. Further, some of the physical propertiesof the polymer are unsatisfactory.

Furthermore, new catalysts produced from a magnesium solid componenthave been proposed for stereospecific polymerization in U.S.applications Ser. Nos. 836,343, 873,630 and 876,823 filed on Sept. 26,1977, Jan. 30, 1978 and Feb. 10, 1978, respectively and now U.S. Pat.Nos. 4,159,965, 4,159,963 and 4,159,256, respectively, the disclosuresof which are incorporated herein by reference. In more detail, amagnesium solid is produced by reaction of a hydrocarbon solubleorganomagnesium with a chlorosilane compound containing a Si--H bond.Said magnesium solid, which does not belong in the category of the abovementioned magnesium compound, is reacted and/or ground with a titaniumcompound and a hydrocarbyl-carboxylic acid or its derivatives. Thus, anobtained product is used as a catalyst component with an organometalcompound together with a hydrocarbon-carboxylic acid or its derivatives.

In view of the foregoing catalysts, it would be highly desirable toprovide a catalyst which has excellent properties and characteristics asabove mentioned, such as high stereoregularity and sufficient activity,and to produce such high quantities of polymer per solid catalystcomponent that it is no longer necessary to remove catalyst residue.

The present invention, in one aspect, is a catalyst useful forpolymerizing olefins comprising a magnesium compound, a titaniumcompound, an electron donor, and an organometallic compound, which ischaracterized in that a solid (1) is obtained by reacting one mole of anorganomagnesium component (i) represented by the general formula

    M.sub.α Mg.sub.β R.sub.p.sup.1 R.sub.q.sup.2 X.sub.4

wherein M is a metal component selected from Al, Zn, B and Be; R¹ and R²are the same or different hydrocarbon groups having 1 to 20 carbonatoms; X is a halogen atom; β is a number greater than zero; α, p, q andr are each numbers zero or greater than zero, respectively, having therelationship of p+q+r=mα+2β; m is a valency of M: or one mol of thereaction product obtained by the reaction of the organomagnesiumcomponent (i) with an electron donor selected from ethers, thioethers,ketones, aldehydes, hydrocarbyl carboxylic acids or derivatives thereof,alcohols, thioalcohols and amines, with 0.01 to 100 mol of chlorosilanecompound (ii) containing Si--H bonds and represented by the generalformula

    H.sub.a SiCl.sub.b R.sub.4.sup.3.sub.-(a+b)

wherein 0<a≦2, b>0, a+b≦4, and R³ is a hydrocarbon group having 1 to 20carbon atoms, that a solid catalyst component (A) is obtained byreacting and/or grinding said solid (1), a titanium compound (2)selected from the halides of tetravalent titanium or trivalent titaniumand a compound (3) selected from nitrogen-containing heterocycliccarboxylic acid esters, sulfur-containing heterocyclic carboxylic acidesters, oxygen-containing heterocyclic carboxylic acid esters andhydrocarbyl carboxylic acid esters, and that said solid catalystcomponent (A) is used with a component (B) comprising an organometalliccompound and a heterocyclic carboxylic acid ester selected fromnitrogen-containing heterocyclic carboxylic acid esters,sulfur-containing heterocyclic carboxylic acid esters andoxygen-containing heterocyclic carboxylic acid esters.

In a second aspect, the invention is a catalyst wherein, as the solidcatalyst component (A) in the above mentioned catalyst system, is usedthe solid catalyst component (A) which is further treated with a halideof tetravalent titanium before combination with (B).

The first feature of the present invention is in that the catalystefficiency based on titanium metal and solid catalyst component isextremely high. For example, as will become clear from Example 24hereinafter described, a catalyst efficiency of 6100g-polypropylene(PP)/g-solid catalyst component or 508000 g-PP/g-Ti wasobtained in the case of propylene polymerization in hexane. In the caseof Example 4, wherein the propylene polymerization was conducted inliquid propylene, a catalyst efficiency of 330,000 g-PP/g-Ti.hour or7600 g-PP/g-solid catalyst component.hour or more was readily attained.Therefore, in Example 24, the Ti-content and Cl-content of polypropyleneat the time of polymerization are about 2 ppm and 55 ppm, respectively.

This indicates that it is no longer necessary to remove the catalystresidue from the propylene prepared by the using this catalyst. In otherwords, the present catalyst is of extremely good performance whichpermits elimination of the catalyst residue removal steps.

The second feature of the present invention is in that higherstereospecifity is achieved in addition to the above mentioned highactivity, the boiling heptane-insoluble portion being as high as 96.4%.

The third is in that when hydrogen is used as a molecular weightregulator in the polymerization process employing the present catalyst,it is possible to carry out the polymerization process in a small amountof hydrogen in order to get a polymer having a desired molecular weight.

The fourth aspect is in that almost no scale deposits on the reactorduring polymerization.

The fifth aspect is in that the obtained polymer is of good grain sizeand polymer powder having a high bulk density can be obtained. Asindicated in the following Examples, densities are 0.43 g/ml or more.

The sixth aspect is in that the angle of repose of the polymer is smalland consequently, handling of the polymer powder is improved.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Each of the component materials and reaction conditions employed for thepreparation of the catalyst will be described hereinafter in detail.

Firstly, explanation will be given with respect to an organomagnesiumcomponent (i) represented by the general formula M.sub.α Mg.sub.β R_(p)¹ R_(q) ² X_(r) (wherein α, β, p, q, r, M, X, R¹ and R² have the samemeanings as described above). This component (i) is shown in the form ofa complex compound of an organomagnesium but includes so-called Grignardcompounds RMgX, R₂ Mg and the complexes of these compounds with othermetallic compounds.

The hydrocarbon groups represented by R¹ and R² in the general formulahave 1 to 20 carbon atoms. They may include aliphatic hydrocarbongroups, alicyclic hydrocarbon groups and aromatic hydrocarbon groupssuch as, for example, methyl, ethyl, propyl, butyl, amyl, hexyl, decyl,cyclohexyl, phenyl and the like. Of these hydrocarbon groups, an alkylgroup is particularly preferred.

As halogen X, fluorine, chlorine, bromine and iodine are used butchlorine is preferable.

As metal atom M, aluminum, zinc, boron and beryllium are preferred forthe reason that these metals easily form a hydrocarbon solubleorganomagnesium complex.

The first component of the organomagnesium component (i) is anorganomagnesium complex which comprises the above mentioned metal (M)and magnesium. A preferred organomagnesium complex, wherein the complexcorresponds to α>0 and r=0 in the general formula, is soluble in aninert hydrocarbon. In these complexes, the ratio of magnesium to metal(β/α) is preferably about 0.1 or more, more preferably at least about0.5 and most preferably in the range of about 1 to 10.

These organomagnesium complexes are synthesized by reacting anorganomagnesium compound R¹ MgX, R₂ ¹ Mg and R¹ R² Mg mentionedhereinafter, with an organometallic compound represented by MR_(m) ² orMR_(m-1) ² H, wherein M, R² and m have the same meanings as abovementioned, in an inert hydrocarbon medium such as hexane, heptane,cyclohexane, benzene, toluene and the like at a temperature in the rangefrom about room temperature to 150° C. Further, the organomagnesiumcomplex also can be prepared by reacting MgX₂ with MR_(m) ², MR_(m-1) ²H, or by reacting R¹ MgX, MgR₂ ¹ with R_(n) ² MX_(m-n) wherein n is anumber of 0 to m.

The preferred second example of the organomagnesium component (i) is ahydrocarbon-soluble magnesium compound MgR_(p) ¹ R_(q) ² whichcorresponds to α=0 and r=0 in the general formula. In the presentinvention it is preferable that the organomagnesium component (i) issoluble in the hydrocarbon solvent.

Therefore, the hydrocarbon-soluble magnesium compound MgR_(p) ¹ R_(q) ²is one of compounds shown in the following three cases:

(a) at least one of R¹ and R² represents a sec- or tert-alkyl grouphaving 4 to 6 carbon atoms;

(b) R¹ and R² represent alkyl groups having a different number of carbonatoms;

(c) at least one of R¹ and R² represents a hydrocarbon group having 6 ormore carbon atoms;

Especially preferable R¹ and R² are one of the following three cases:

(a)' R¹ and R² both are hydrocarbon groups having 4 to 6 carbon atoms,and at least one of them is a sec- or tertalkyl group;

(b)' R¹ is an alkyl group having 2 to 3 carbon atoms, and R² is an alkylgroup having at least 4 carbon atoms; and

(c)' R¹ and R² both are alkyl groups having at least 6 carbon atoms.

In case of (a) and (a)', exemplary groups include sec--C₄ H₉, tert--C₄H₉, --CH(C₂ H₅)₂, --C(C₂ H₅) (CH₃)₂, --CH(CH₃)(C₄ H₉), --CH(C₂ H₅)(C₃H₇), --C(CH₃)₂ (C₃ H₇), --C(CH₃)(C₂ H₅)₂ and the like. A sec-alkyl groupis preferred and sec-C₄ H₉ is especially preferred.

In a case of (b) and (b)', ethyl and propyl are preferred alkyl groups,and ethyl is most preferred. Exemplary alkyl groups having 4 or morecarbon atoms include butyl, amyl, hexyl, octyl and the like. Butyl andhexyl are preferred.

In case of (c) and (c)', hydrocarbon groups having at least 6 carbonatoms include hexyl, octyl, decyl, phenyl and the like. An alkyl groupis preferred. Hexyl is most preferred.

Therefore, an exemplary hydrocarbon-soluble magnesium compound R_(p) ¹R_(q) ² Mg includes (sec--C₄ H₉)₂ Mg, (tert--C₄ H₉)₂ Mg, n--C₄ H₉ MgC₂H₅, n--C₄ H₉ Mgsec--C₄ H₉, n--C₄ H₉ Mgtert--C₄ H₉, n--C₆ H₁₃ MgC₂ H₅,n--C₈ H₁₇ MgC₂ H₅, (n--C₆ H₁₃)₂ Mg, (n--C₈ H₁₇)₂ Mg, (n--C₁₀ H₂₁)₂ Mgand the like.

A third exemplary organomagnesium compound within formula (i) is R¹ MgXcorresponds to α=0, β=1, q=0, r=1 in the general formula and is wellknown as a Grignard compound. Gnerally, the Grignard compound issynthesized not only in ether solution but also in hydrocarbon solvent.In the present invention, compounds provided both ways are employed asthe organomagnesium component (i). There are, for example, methylmagnesium chloride, methyl magnesium bromide, methyl magnesium iodide,ethyl magnesium chloride, ethyl magnesium bromide, ethyl magnesiumiodide, n- or iso-propyl magnesium chloride, n- or iso-propyl magnesiumbromide, n- or iso-propyl magnesium iodide, n-butyl magnesium chloride,n-butyl magnesium bromide, n-butyl magnesium iodide, sec- or tert-butylmagnesium chloride, sec- or tert-butyl magnesium bromide, sec- ortert-butyl magnesium iodide, n-amyl magnesium chloride, n-amyl magnesiumbromide, hexyl magnesium chloride, hexyl magnesium bromide, octylmagnesium chloride, phenyl magnesium chloride, phenyl magnesium bromideand ether coordinate complexes with one of these compounds. Such etherincludes dimethylether, diethylether, diisopropylether, dibutylether,diallylether, tetrahydrofuran, dioxane, anisole and the like.

In the present invention, the organomagnesium component (i) is used,itself, as a reaction agent to be reacted with a chlorosilane compound(ii). However, the reaction product of the organomagnesium component (i)and an electron donor can be also employed. In this case, theorganomagnesium component (i) is preferably a hydrocarbon solublecompound or complex such as R¹ R² Mg, R₂ ¹ Mg and M.sub.α MgR_(p) ¹R_(q) ². The electron donor should be selected from ethers, thioethers,ketones, aldehydes, carboxylic acids or derivatives thereof, alcohols,thioalcohols and amines. All these electron donors are well knowncompounds.

For example, the ether is shown by the general formula ROR' wherein Rand R' include aliphatic, aromatic and alicyclic hydrocarbon groupshaving 1 to about 20 carbon atoms. Exemplary groups may be methyl,ethyl, propyl, butyl, amyl, hexyl, decyl, octyl, dodecyl, cyclohexyl,phenyl, benzyl and the like.

The thioether is shown by the general formula RSR' (wherein R and R'have the same meanings as mentioned for ROR') and the exemplary groupsare the same as described in RSR'.

The ketones are shown by the general formula RCOR' (wherein R and R'have the same meanings as described for ROR'). Exemplary groups aremethyl, ethyl, propyl, butyl, hexyl, cyclohexyl, phenyl and the like. Ofthese compounds, dimethyl ketone and diethyl ketone are preferred.

As the aldehydes are also used well known aliphatic, aromatic andalicyclic aldehydes having 1 to about 20 carbon atoms.

As the hydrocarbyl carboxylic acid or derivatives thereof are usedaliphatic, alicyclic and aromatic, saturated and unsaturated carboxylicacids, wherein the number of carbon atoms of the carboxylic acids canvary widely, but may be 1 to about 20, their acid anhydrides, theiresters, their carboxylic halides and their acid amides. Exemplaryhydrocarbyl carboxylic acids include formic acid, acetic acid, propionicacid, butyric acid, valeric acid, oxalic acid, malonic acid, succinicacid, maleic acid, acrylic acid, benzoic acid, toluic acid, terephthalicacid, etc. As hydrocarbyl carboxylic anhydrides, for example, aceticanhydride, propionic anhydride, n-butyric anhydride, succinic anhydride,maleic anhydride, benzoic anhydride, phthalic anhydride, etc. arepreferable. As hydrocarbyl carboxylic acid esters, the alcohol of theester group may include 1 to about 20 carbon atoms, for example, emthylor ethyl formate, methyl, ethyl or propyl acetate, methyl, ethyl, propylor butyl propionate, ethyl butyrate, ethyl valerate, ethyl caproate,ethyl n-heptanoate, dibutyl oxalate, ethyl succinate, ethyl malonate,dibutyl malate, methyl or ethyl acrylate, methyl methacrylate, methyl,ethyl, propyl or butyl benzoate, methyl, ethyl, propyl, butyl or amyltoluate, methyl, or ethyl p-ethylbenzoate, methyl, ethyl, propyl orbutyl anisate, methyl or ethyl p-ethoxybenzoate. As hydrocarbylcarboxylic halides are preferably used carboxylic chlorides such asacetyl chloride, propionyl chloride, butyryl chloride, succinoylchloride, benzoyl chloride, tolyl chloride, etc. As hydrocarbylcarboxylic amides are used dimethyl formamide, dimethyl acetamide,dimethyl propionamide, etc.

The alcohols and thioalcohols used are also well known aliphatic,aromatic, alicyclic compounds having 1 to about 20 carbon atoms.Exemplary alcohols include methyl alcohol, ethyl alcohol, propylalcohol, butyl alcohol, amyl alcohol, hexyl alcohol, phenol, cresol andthe like, preferably sec- or tert-alcohols or aromatic alcohols such assec-propyl alcohol, sec-butyl alcohol, tert-butyl alcohol, sec-amylalcohol, tertamyl alcohol, sec-hexyl alcohol, phenol, o,m,p-cresol, etc.Exemplary thioalcohols include methyl mercaptan, propyl mercaptan, butylmercaptan, amyl mercaptan, hexyl mercaptan, phenyl mercaptan, etc. Sec-,tert- or aromatic thioalcohols are preferred.

The amines include aliphatic, alicyclic or aromatic amines having 1 toabout 20 carbon atoms. They are preferably sec- or tert-amines such astrialkyl amine, triphenyl amine, pyridine, etc.

The reaction between the organomagnesium component (i) and the electrondonor is conducted in an inert hydrocarbon medium such as aliphatic,aromatic or alicyclic hydrocarbons and their mixtures. The reactionorder of these compounds is optional. For example, the electron donor isadded to the organomagnesium component (i), or vice versa, or bothcomponents are simultaneously added to a reaction zone. In thesereactions, the amount of the electron donor is not limited, butpreferably is less than about 1 mol, more preferably in the range ofabout 0.01 to 0.8 mol, most preferably about 0.05 to 0.5 mol based on 1mol of the organomagnesium component (i).

The above mentioned organomagnesium component (i) or the reactionproduct of the organomagnesium component (i) with the electron donor isused to produce the solid (1) by reaction with a chlorosilane compound(ii) containing Si-H bonds, represented by the general formula H_(a)SiCl_(n) R₄₋(a+b)³.

In the general formula, a, b and R³ have the same meanings as mentionedabove, and hydrocarbon groups represented by R³ have 1 to 20 carbonatoms. They include aliphatic-, alicyclic- or aromatic-hydrocarbongroups such as methyl, ethyl, propyl, butyl, amyl, hexyl, decyl,cyclohexyl, phenyl and the like. Preferably the hydrocarbon group is analkyl group having 1 to 10 carbon atoms and a lower alkyl group such asmethyl, ethyl, propyl is particularly preferred. The range of the valueof a and b is defined by a>0, b>0, a+b≦4 and 0<a≦2. The exemplarychlorosilane compound includes HSiCl₃, HSiCl₂ CH₃, HSiCl₂ C₂ H₅, HSiCl₂n--C₃ H₇, HSiCl₂ i--C₃ H₇, HSiCl₂ n--C₄ H₉, HSiCl₂ C₆ H₅, HSiCl₂(4-Cl-C₆ H₄), HSiCl₂ CH═CH₂, HSiCl₂ CH₂ C₆ H₅, HSiCl₂ (1--C₁₀ H₇),HSiCl₂ CH₂ CH═CH₂, H₂ SiClCH₃, H₂ SiCl₂ C₂ H₅, HSiCl(CH₃)₂, HSiClCH₃(i--C₃ H₇), HSiClCH₃ (C₆ H₄), HSiCl(C₆ H₅)₂, and the like. This compoundalone, a mixture of these compounds or a mixture partially containingany of these compounds is used. Preferred chlorosilane compounds aretrichlorosilane, monomethyldichlorosilane, dimethylchlorosilane, andethyldichlorosilane. Especially preferred chlorosilanes aretrichlorosilane and monomethyldichlorosilane. In these compounds, it isimportant there is a Si-H bond. As evidenced by specific examples andcomparative examples, preferred results cannot be obtained with silanecompounds containing no Si--H bonds.

Hereinafter, the reaction between the organomagnesium component (i) andthe chlorosilane compound (ii) is illustrated.

The reaction is conducted in an inert medium such as aliphatichydrocarbon (e.g., hexane, heptane, etc.), aromatic hydrocarbon (e.g.,benzene, toluene, xylene, etc.), alicyclic hydrocarbon (e.g.,cyclohexane, methyl cyclohexane, etc.), ether (e.g., ether,tetrahydrofuran, etc.) or mixtures.

Of these media, aliphatic hydrocarbons are preferable from the point ofcatalyst performance. With regard to the reaction temperature, there isnot particular limitation but from the point of reasonable reactionrate, the reaction is preferably carried out at a temperatures of about40° C. or more. The reaction ratio of the two components is notparticularly limited, but it is recommended to use about 0.01 to 100mol, preferably about 0.1 to 10 mol of the chlorosilane compound (ii)per 1 mol of magnesium in the organomagnesium component (i).

As to the manner of the reaction, it can involve (i) simultaneouslyintroducing the two components, [i.e., (i) and (ii)] into a reactionzone, (ii) previously charging the chlorosilane compound into thereaction zone, then introducing the organomagnesium component to thereaction zone to react therein, or (iii) previously charging theorganomagnesium component, then introducing the chlorosilane compound.The latter two methods are preferable, with method (ii) providingparticularly good results.

Where organomagnesium component (i) is insoluble, it is also possible toconduct the reaction heterogeneously in a reaction zone using thechlorosilane compound (ii) as reactant. In this case, too, the aforesaidconditions are preferred as to temperature, reaction ratio and themanner of reaction.

The structure and the composition of the solid (1) obtained according tothe above-mentioned reaction, may vary according to the starting rawmaterials, and reaction conditions, but the analytical value shows thatthe solid (1) is a magnesium compound containing a halogen atom andabout 0.1-2.5 millimol of hydrocarbon group having a Mg--C bond per gsolid material. This solid (1) has an extremely large specific surfacearea showing a value as high as about 100-300 m² /g according to themeasurement by B.E.T. method. The solid (1) has an extremely highersurface area compared with a conventional magnesium halide solid and itis a characteristic feature that said solid (1) is an active magnesiumcompound containing a hydrocarbon group and possessing reducing power.

Further description will be made with regard to the tetra or trivalenttitanium halide (2) which is a raw material of the solid catalystcomponent (A) as well as the above mentioned solid (1) and heterocyclicor hydrocarbyl carboxylic acid ester (3) described hereinafter.

As the tetravalent titanium halide, there are included titanium halides,titanium alkoxyhalides and mixtures thereof such as titaniumtetrachloride, titanium tetrabromide, titanium tetraiodide,trimethoxytitanium chloride, dimethoxytitanium dichloride,methoxytitanium trichloride, triethoxytitanium chloride,diethoxytitanium dichloride, ethoxytitanium trichloride,tripropoxytitanium chloride, dipropoxytitanium dichloride,propoxytitanium trichloride, butoxytitanium trichloride,dibutoxytitanium dichloride, tributoxytitanium monochloride, etc.

As the halides of trivalent titanium, there may be used titaniumtrichloride, titanium tribromide, titanium triiodide and a solidsolution containing one of these components such as a solid solution oftitanium trichloride and aluminum trichloride, a solid solution oftitanium tribromide and aluminum tribromide, a solid solution oftitanium trichloride and vanadium trichloride, a solid solution oftitanium trichloride and ferric chloride, a solution solution oftitanium trichloride and zirconium trichloride, etc. Preferred trivalenttitaniums are titanium trichloride and a solid solution of titaniumtrichloride and aluminum trichloride (TiCl₃.1/3AlCl₃).

Description will now be given with regard to the component (3) selectedfrom a nitrogen-containing heterocyclic carboxylic acid ester,sulfur-containing heterocyclic carboxylic acid ester, oxygen-containingheterocyclic carboxylic acid ester and hydrocarbyl carboxylic acidester.

The preferred heterocyclic carboxylic acid esters are the compoundswherein a carboalkoxy group having 2 to about 20 carbon atoms is bondedon the heterocyclic ring.

As N-containing heterocyclic carboxylic acid esters, for example, arementioned pyrrol-carboxylic acid esters, indole-carboxylic acid esters,carbazole-carboxylic acid esters, oxazole-carboxylic acid esters,thiazole-carboxylic acid esters, imidazole-carboxylic acid esters,pyrazole-carboxylic acid esters, pyridine-carboxylic acid esters,phenanthridinecarboxylic acid esters, anthrazoline-carboxylic acidesters, phenanthroline-carboxylic acid esters, naphthylidine-carboxylicacid esters, oxadine-carboxylic acid esters, thiazine-carboxylic acidesters, pyridazine-carboxylic acid esters, pyrimidine-carboxylic acidesters, pyrazine-carboxylic acid esters, and the like. Exemplarypreferred compounds are pyrrol-2-carboxylic acid methyl, ethyl, propylor butyl ester, pyrrol-3-carboxylic acid methyl, ethyl, propyl or butylester, pyridine-2-carboxylic acid methyl, ethyl, propyl, butyl or amylester, pyridine-3-carboxylic acid methyl, ethyl, propyl, butyl or amylester, pyridine-4-carboxylic acid methyl, ethyl, propyl, butyl or amylester, pyridine-2,3-dicarboxylic acid methyl or ethyl ester,pyridine-2,5-dicarboxylic acid methyl or ethyl ester,pyridine-2,6-dicarboxylic acid methyl or ethyl ester,pyridine-3,5-dicarboxylic acid methyl or ethyl ester,quinoline-2-carboxylic acid methyl or ethyl ester,dimethylpyrrol-carboxylic acid ethyl ester, N-methylpyrrol-carboxylicacid ethyl ester, 2-methylpyridine-carboxylic acid ethyl ester,piperidine-2-carboxylic acid ethyl ester, piperidine-4-carboxylic acidethyl ester, pyrrolidine-2-carboxylic acid ethyl ester, L-proline ethylester, isonipecotinic acid ethyl ester, D,L-pipecolinic acid ethylester, nipecotinic acid ethyl ester, etc.

As S-containing heterocyclic carboxylic acid esters, for example, thereare mentioned thiophenecarboxylic acid esters, thianaphthene carboxylicacid esters, isothianaphthene carboxylic acid esters, benzothiophenecarboxylic acid esters, phenoxathiin carboxylic acid esters, benzothianecarboxylic acid esters, thiaxanthene carboxylic acid esters, thioindoxylcarboxylic acid esters and the like. Exemplary preferred compounds are2-thiophenecarboxylic acid methyl, ethyl, propyl, butyl or amyl ester,3-thiophenecarboxylic acid methyl, ethyl, propyl, butyl or amyl ester,2,3-thiophenedicarboxylic acid methyl or ethyl ester, B2,4-thiophenedicarboxylic acid methyl or ethyl ester,2,5-thiophenedicarboxylic acid methyl or ethyl ester, 2-thienyl-aceticacid methyl, ethyl, propyl or butyl ester, 2-thienylacrylic acid methylor ethyl ester, 2-thienylpyruvic acid methyl or ethyl ester,2-thianaphthene carboxylic acid methyl or ethyl ester, 3-thianaphthenecarboxylic acid methyl or ethyl ester, 3-hydroxy-2-thianaphthenecarboxylic acid methyl or ethyl ester, 2,3-thianaphthene dicarboxylicacid methyl or ethyl ester, 2-thianaphthenyl acetic acid methyl or ethylester, 3-thianaphthenyl acetic acid methyl or ethyl ester,2-benzothiophene carboxylic acid methyl or ethyl ester, 3-benzothiophenecarboxylic acid methyl or ethyl ester, 4-benzothiophene carboxylic acidmethyl or ethyl ester, 1-phenoxathiin carboxylic acid methyl or ethylester, 2-phenoxathiin carboxylic acid methyl or ethyl ester,3-phenoxathiin carboxylic acid methyl or ethyl ester and the like. Ofthese exemplary compounds, preferred compounds include2-thiophenecarboxylic acid methyl, ethyl, propyl or butyl ester,3-thiophene carboxylic acid methyl or ethyl ester, 2-thienyl acetic acidmethyl or ethyl ester, 2-thienylacrylic acid methyl or ethyl ester,2-thianaphthene carboxylic acid methyl or ethyl ester and the like.

As oxygen-containing heterocyclic carboxylic acid esters, for example,there are mentioned furan carboxylic acid esters, dihydrofurancarboxylic acid esters, benzofuran carboxylic acid esters, coumarancarboxylic acid esters, pyran carboxylic acid esters, pyrone carboxylicacid esters, coumalic acid esters, isocoumalic acid esters and the like.Exemplary preferred compound include 2-furan carboxylic acid methyl,ethyl, propyl or butyl ester, 3-furan carboxylic acid methyl ethyl,propyl or butyl ester, 2,3-furan dicarboxylic acid methyl ester,2,4-furan dicarboxylic acid methyl ester, 2,5-furan dicarboxylic acidmethyl ester, 3,4-furan dicarboxylic acid methyl ester,4,5-dihydro-2-furan carboxylic acid methyl ester,tetrahydrofuran-2-carboxylic acid methyl ester, coumarilic acid methylester (2-benzofuran carboxylic acid methyl ether), coumaran-2-carboxylicacid ethyl ester, coumalic acid methyl or ethyl ester,5-hydroxy-4-ethoxycarboxyl coumarin, 4-ethoxycarbonyl isocoumarin,3-methyl-2-furan carboxylic acid ethyl ester, isodehydroacetic acid,etc. Of these preferred compounds are 2-furan carboxylic acid methyl,ethyl, propyl or butyl ester, 3-furan carboxylic acid methyl, ethyl,propyl or butyl ester, 4,5-dihydro-2-furan carboxylic acid methyl orethyl ester, 2-tetrahydrofuran carboxylic acid methyl ester, coumalicacid methyl or ethyl ester, etc.

The hydrocarbyl carboxylic acid ester includes aliphatic, aromatic oralicyclic hydrocarbon carboxylic acid esters, wherein a preferredcompound comprises a carboalkoxy group having 2 to about 20 carbon atomsand a hydrocarbon group having 1 to about 20 carbon atoms. Exemplarycarboxylic acid esters are ethyl formate, methyl acetate, ethyl acetate,n-propyl acetate, ethyl propionate, ethyl butyrate, ethyl valerate,ethyl capronate, ethyl n-heptanoate, di-n-butyl oxalate, monoethylsuccinate, diethyl succinate, ethyl malonate, di-n-butyl malate, methylacrylate, ethyl acrylate, methyl methacrylate, methyl benozate, ethylbenzoate, n- or iso-propyl benzoate, n-, iso-, sec- or tert-butylbenzoate, methyl p-toluate, ethyl p-toluate, n- or iso-propyl p-toluate,n- or iso-amyl p-toluate, ethyl o-toluate, ethyl m-toluate, methylp-ethylbenzoate, ethyl o-ethylbenzoate, methyl anisate, ethyl anisate,n- or iso-propyl anisate, methyl p-ethoxybenzoate, ethylp-ethoxybenzoate, methyl terephthalate, etc. Of these compounds,preferred are methyl benzoate, ethylbenzoate, methyl p-toluate, ethylp-toluate, methyl anisate, ethyl anisate and the like.

Description will be given with regard to the synthesis of solid catalystcomponent (A) obtained by reacting and/or grinding the above-mentionedsolid material (1), titanium compound (2) and compound (3) selected fromN, S or O-- containing heterocyclic carboxylic acid esters orhydrocarbyl carboxylic acid esters.

For the reaction and/or grinding of the above mentioned solid (1), thetitanium compound (2) and the carboxylic acid ester (3), any of themethods can be adopted such as [1] a method in which a titanium compoundand a carboxylic acid ester are reacted in a liquid or gas phase, or [2]a method in which a liquid or gas phase reaction and/or grinding arecombined.

The method [1] includes a process of simultaneous reaction of the solid,titanium compound and carboxylic acid ester (method 1 ), a process ofreacting the solid and a titanium compound followed by the reaction witha carboxylic acid ester (method 2 ), and a process of first reacting thesolid and the carboxylic acid ester followed by reaction with a titaniumcompound (method 3 ). Although any of these methods may be employed, thelatter two methods, especially method 3 , are preferred.

With regard to the method [2], three cases, i.e., where the titaniumcompound has the valence of 4 (I), valence of 3 (II), and valences ofboth 3 and 4 (III), are hereinafter described.

In the case of (I), there are mentioned, grinding the solid obtained bysimultaneously reacting the above mentioned solid (1), tetravalenttitanium compound (2-1) and carboxylic acid ester (3) (synthesis 1 ),grinding the solid obtained by first reacting the above mentioned solid(1) and the tetravalent titanium compound (2-1) followed by furtherreaction with the carboxylic acid ester (3) (synthesis 2 ), and grindingthe solid obtained by first reacting the above mentioned solid (1) andthe carboxylic acid ester (3) thereof followed by reaction with thetetravalent titanium compound (2-1) (synthesis 3 ). Any of them may beemployed but the latter two methods are preferred. Especially synthesis3 gives favorable results.

In the case of trivalent titanium compound (II), various methods arepossible for preparing a solid catalyst (A) from said solid (1), atrivalent titanium compound (2-2) and a carboxylic acid ester (3), butespecially the following three methods give favorable results; namely amethod wherein the three components are ground together (synthesis 1 ),a method wherein the solid (1) and the carboxylic acid ester (3) arefirst contacted and then mechanical grinding is carried out after theaddition of the trivalent titanium compound (2-2) (synthesis 2 ), and amethod wherein the solid (1) and the trivalent titanium compound (2-2)are mechanically ground, followed by the treatment with a carboxylicacid ester (3) (synthesis 3 ).

In the case of both tetra and trivalent titanium compound (III), amethod wherein the solid (1), a tetravalent titanium compound (2-1), atrivalent titanium compound (2-2), and a carboxylic acid ester (3) aresimultaneously ground (synthesis 1 ), a method wherein solid obtained byreacting (1) and (2-1) is treated with (3) followed by grinding thereoftogether with (2-2) (synthesis 2 ), a method wherein solid obtained byreacting (1) and (3) is treated with (2-1) followed by grinding thereoftogether with (2-2) (synthesis 3 ), a method wherein solid obtained byreacting (1) and (2-1), is ground after addition of (2-2) and (3)(synthesis 4 ), and the like may be mentioned. Among them, synthesis 3is preferred.

Further, by treating the solid catalyst component (A) prepared by themethod [1] and [2] described above with a tetravalent titanium compound(4) containing at least one halogen atom, further increase of catalystefficiency, i.e., the first feature of the present invention, isattained. A tetravalent titanium compound (2-1) mentioned above isemployed as a tetravalent titanium compound (4), and titaniumtetrahalide, especially titanium tetrachloride, is preferred.

Firstly, among the methods wherein solid catalyst component (A)synthesized by the method [1] is treated with the above mentionedhalogenated tetravalent titanium, there are included a method oftreating the solid catalyst component (A) obtained by the method [1]- 1, [1]- 2 and [1]- 3 , with the tetravalent titanium.

Next, with regard to the method wherein the solid catalyst component (A)synthesized according to method [2] is further treated with atetravalent titanium halide, explanation will be given for (I), (II) and(III).

In the case of (I), there are three possible methods wherein the solidcatalyst component (A) synthesized according to [2]-(I)- 1 , [2]-(1)- 2and [2]-(I)- 3 are respectively treated with a tetravalent titaniumhalide, but the latter two methods are preferred.

In the case of (II), there are four possible methods wherein the solidcatalyst component (A) synthesized according to the methods [2]-(II)- 1, [2]-(II)- 2 , [2]-(II)- 3 and [2]-(II)- 4 are respectively treatedwith a tetravalent titanium halide.

In the case of (III), there may be mentioned a method wherein a solid(1), a tetravalent titanium compound (2-1), a trivalent titaniumcompound (2-2), and a carboxylic acid ester (3) are simultaneouslyground, followed by the treatment with a tetravalent titanium halide(synthesis 1 ), a method wherein the solid obtained by reacting (1) and(2-1) is treated with (3), ground together with (2-2) and treated with atetravalent titanium halide (synthesis 2 ), a method wherein the solidobtained by reacting (1) and (3) is treated with (2-1), ground togetherwith (2-2), and further treated with a tetravalent titanium halide(synthesis 3 ), a method wherein the solid obtained by reacting (1) and(2-1) is ground together after addition of (2-2) and (3) and furthertreated with a tetravalent titanium halide (synthesis 4 ). Among them,the methods 2 , 3 and 4 are preferred.

Next, the operating conditions of reacting and/or grinding theabove-mentioned solid, titanium compound, and carboxylic ester will beexplained.

(i) Firstly explanation will be made with regard to the reaction betweena solid (1) [obtained by reacting an organomagnesium component (i) and achlorosilane compound (ii)] or a reaction product of this solid (1) anda carboxylic acid ester (3), and a titanium compound (2).

The reaction may be carried out using an inert reaction medium or usingan undiluted titanium compound per se as a reaction medium without usingan inert reaction medium. As an inert reaction medium, for example,there may be mentioned aliphatic hydrocarbons such as hexane andheptane, aromatic hydrocarbons such as benzene, toluene, and xylene,alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, andthe like, among which aliphatic hydrocarbons are preferred. The reactiontemperature and the concentration of the titanium compound, though notspecifically limited, are preferably in the range of 80° C. or higherand about 2 mol/l of the titanium compound or higher, respectively.Still more preferably, undiluted titanium compound per se is used forcarrying out the reaction as a reaction medium. With regard to areaction mole ratio, excess titanium compound relative to the magnesiumcomponent in the solid gives good results.

(ii) Secondly, explanation will be given about the reaction between asolid (1) [obtained by reacting an organomagnesium component (i) and achlorosilane compound (ii)], or a reaction product of this solid (1)with a titanium compound (2) and a carboxylic acid ester (3).

The reaction is carried out using an inert reaction medium. As the inertreaction medium, any of the above mentioned aliphatic, aromatic oralicyclic hydrocarbons may be used. The reaction temperature, though notspecifically limited, preferably ranges from room temperature to 100° C.In case a solid (1) and a carboxylic acid ester (3) are reacted, theratio of the two components is not specifically limited. However, it isrecommended that the amount of carboxylic acid ester ranges between0.001 mol-50 mols, preferably 0.005 mol-10 mols relative to one mol ofhydrocarbon group contained in the solid (1). In case the reactionproduct of the solid (1) and a titanium compound (2) is reacted with acarboxylic acid ester (3), a ratio of the two components ranging 0.01mol-100 mols, preferably 0.1 mol-10 mols of the amount of carboxylicacid ester relative to one mol of titanium atom in the solid (1) isrecommended.

(iii) Thirdly, explanation will be given with regard to the method ofgrinding the solid formed according to the above mentioned reactions(i)-(ii). As a grinding means, well known mechanical grinding means suchas a rotary ball mill, a vibration ball mill, an impact ball mill, andthe like may be employed. Grinding time is in the range of 0.5-100hours, preferably 1-30 hours, and grinding temperature is in the rangeof 0°-200° C., preferably 10°-150° C.

(iv) Fourthly, explanation will be given with respect to the treatmentof the solid catalyst component (A) obtained according to (i)-(iii) witha tetravalent titanium compound. The reaction is carried out using aninert reaction medium or utilizing the titanium compound itself as areaction medium. As an inert reaction medium, there may be mentioned,for example, aliphatic hydrocarbons such as hexane or heptane, aromatichydrocarbons such as benzene, toluene, etc., and alicyclic hydrocarbonssuch as cyclohexane, methylcyclohexane, etc., but aliphatic hydrocarbonsare preferred. The concentration of the titanium compound is preferably2 mol/l or higher; especially preferred is the use of the titaniumcompound itself as a reaction medium. Although the reaction temperatureis not specifically limited, good results are obtained when reaction isconducted at a temperature of 80° C. or higher.

Although the composition and the structure of the solid catalystcomponent (A) obtained according to the above mentioned reactions (i) to(iv) vary depending on starting material and reaction conditions, it wasfound from the analysis of the composition that the solid catalystcomponent (A) contains approximately 1-10 percent by weight of titaniumand has a surface area of 50-300 m² /g.

Organometallic compounds used as component (B) are compounds of metalsof Groups I-III of the Periodic Table and especially an oranoaluminumcompound is preferred. As organoaluminum compounds, those represented bythe general formula AlR_(t) ⁴ Z_(3-t) (wherein R⁴ is a hydrocarbon grouphaving 1-20 carbon atoms, Z is a member selected from hydrogen, halogen,alkoxy, aryloxy and siloxy, and t is 2-3) are used individually or as amixture. In the above formula, hydrocarbon groups having 1-20 carbonatoms and represented by R⁴ include aliphatic hydrocarbons, aromatichydrocarbons and alicyclic hydrocarbons.

Specifically, for example, triethylaluminum, tri-n-propylaluminum,triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum,trihexylaluminum, trioctylaluminum, tridecylaluminum,tridodecylaluminum, trihexadecylaluminum, diethylaluminum hydride,diisobutylaluminum hydride, diethylaluminum ethoxide, diisobutylaluminumethoxide, dioctylaluminum butoxide, diisobutylaluminum octyloxide,diethylaluminum chloride, diisobutylaluminum chloride,dimethylhydrosiloxyaluminum dimethyl, ethylmethylhydrosiloxyaluminumdiethyl, ethyldimethylsiloxyaluminum diethyl, aluminum isoprenyl and thelike, and mixtures thereof are recommended.

A combination of these alkylaluminum compounds with the above mentionedsolid catalyst component (A) provides a highly active catalyst, andespecially trialkylaluminum and dialkylaluminum hydride are preferredbecause they have the highest activity.

The nitrogen-containing heterocyclic carboxylic acid ester,sulfur-containing heterocyclic carboxylic acid ester andoxygen-containing heterocyclic carboxylic acid ester to be used with anorganometallic compound (B) may be the same as or different from thecompound used for preparation of the solid catalyst component (A). As tothe manner of addition of the heterocyclic carboxylic acid ester and theorganometallic compound, the two components may be mixed prior topolymerization or they may be added to the polymerization systemseparately. Especially preferred is to add separately the previouslyprepared reaction product of an organometallic compound and aheterocyclic carboxylic acid ester and an organometallic compound to thepolymerization system.

The ratio of the heterocyclic carboxylic acid ester amounts to less thanabout 10 mol, preferably about 0.01 mol to 1 mol relative to one mol ofthe organometallic compound.

The catalyst components of the present invention comprising the solidcatalyst component (A) and the component (B) of an organometalliccompound incorporated with a heterocyclic carboxylic acid ester may beadded to the polymerization system separately or may be blended prior tothe polymerization.

The ratio of the component comprising an organometallic compound with aheterocyclic carboxylic acid ester relative to 1 gram of the solidcatalyst component preferably ranges from about 1 millimol to 3000millimol.

The present invention relates to highly active catalysts for highlystereospecific polymerization of olefins. Especially the presentinvention is suitable for polymerizing stereoregularly propylene,butene-1, pentene-1, 4-methylpentene-1, 3-methylbutene-1 and likeolefins. Also it is suitable for copolymerizing said olefins withethylene or other olefins. Further it is suitable for polymerizingethylene with better efficiency. It is also possible in the presentinvention to add hydrogen, a halogenated hydrocarbon or anorganometallic compound which is liable to cause chain transfer in orderto regulate the molecular weight of the polymer.

As to the manner of polymerization, a usual suspension polymerization, abulk polymerization in liquid monomers, or a gas phase polymerizationcan be employed. Suspension polymerization may be carried out at roomtemperature-150° C. by introducing the catalyst together with apolymerization solvent e.g., an aliphatic hydrocarbon such as hexane orheptane, an aromatic hydrocarbon such as benzene, toluene or xylene, oran alicyclic hydrocarbon such as cyclohexane or methylcyclohexane, andintroducing an olefin such as propylene under a pressure of 1-20 kg/cm²under inert atmosphere. Bulk polymerization of olefins may be carriedout with an olefin such as propylene being in the liquid state using acatalyst and the liquid olefin as a polymerization solvent. For example,propylene can be polymerized in propylene itself under a pressure of10-45 kg/cm² at a temperature of from room temperature to 90° C. On theother hand, gas phase polymerization can be carried out, e.g., under apressure of 1-50 kg/cm² and at a temperature ranging from roomtemperature to 120° C. in the absence of a solvent, by means of afluidized bed, a movable bed or mechanical stirrer so that the olefinsuch as propylene and the catalyst can be well contacted.

Hereinafter the present invention will be explained by examples. In theexamples, insoluble matter of n-heptane extraction means the residueleft after six hour extraction of polymer with boiling n-heptane, andmelt flow index (MFI) is measured according to ASTM D1238, whereintemperature and load are 230° C. and 2.16 kg, respectively. Angle ofrepose is measured according to bulk density.

EXAMPLE 1 (I) Synthesis of hydrocarbon soluble organomagnesium complex

Di-n-butyl magnesium (138.0 g) and triethylaluminum (19.0 g) werecharged into a 2 l volume flask, purged with nitrogen, together withheptane (1 l) and reacted at 80° C. for two hours to obtain a solutionof an organomagnesium complex. Analysis showed that the complex had acomposition of AlMg₆.0 (C₂ H₅)₂.9 (n--C₄ H₉)₁₂.1 and the concentrationof the organometal was 1.25 mol/l.

(II) Preparation of a solid material by the reaction with a chlorosilanecompound

Oxygen and moisture in a 2 l volume flask fitted with a dropping funnelwere purged with nitrogen and, under nitrogen atmosphere, one liter ofheptane containing 1 mol of trichlorosilane (HSiCl₃) was charged to theflask and heated to 65° C. Next, 500 mmol of the solution of saidorganomagnesium complex was added thereto dropwise with stirring overone hour, and further reacted therewith at this temperature for onehour. The resultant insoluble white precipitate was isolated, washedwith n-hexane, and dried to obtain 42.5 g of a white solid material(A-1). Analysis showed that 1 g of this solid contained 9.16 mmol of Mg,19.20 mmol of Cl, 1.70 mmol of Si and 0.58 mmol of alkyl group, and thespecific surface area measured by the B.E.T. method was 269 m² /g.

(III) Preparation of a solid catalyst component

To a 2 l vessel fully purged with nitrogen, 20 g of the above whitesolid material (A-1) was added together with 600 ml of n-hexane and 15.0mmol of 2-thiophenecarboxylic acid ethyl ester. The mixture was reactedwith stirring one hour at 80° C. to obtain solid (B-1). To a pressureproof vessel having been purged with nitrogen was charged 18 g of thesolid (B-1) and 300 ml of titanium tetrachloride. After reaction wasconducted with stirring at 130° C. for two hours, the solid portion wasisolated by filtration, washed thoroughly with hexane, and dried, and asolid catalyst component (S-1) was obtained. Analysis of this solidshowed that it contains 2.2% by weight of Ti.

(IV) Slurry polymerization of propylene

The solid catalyst component (80 mg) synthesized in (III), above, 2.4mmol of triethylaluminum and 0.8 mmol of 2-thiophenecarboxylic acidethyl ester were charged together with 0.8 liter of hexane into a1.5-liter autoclave, the inside of which had been purged with nitrogenand deaerated in vacuo. While the temperature inside the autoclave wasbeing maintained at 60° C., propylene were pressurized to 5.0 kg/cm² sothat a total gauge pressure of 4.8 kg/cm² could be achieved.Polymerization was allowed to proceed for two hours by supplyingpropylene, while maintaining a total gauge pressure of 4.8 kg/cm². Therewere obtained 170 g of a hexane-insoluble polymer and 6.2 g of ahexane-soluble polymer.

Catalyst yield was 9660 g-PP/g of Ti.hr.propylene pressure. After thehexane-insoluble polymer was extracted with boiling heptane, theremaining portion was 95.7%.

EXAMPLE 2 (I) Synthesis of a hydrocarbon-soluble organomagnesium complex

Di-n-butyl-magnesium (138.0 g) and 19.0 g of triethylaluminum were takenup in a 2-liter flask having been purged with nitrogen, together with 1liter of n-heptane. The mixture was reacted with stirring at 80° C. for2 hours to obtain an organomagnesium complex solution. Analysis of thiscomplex revealed that it had the composition AlMg₆.0 (C₂ H₅)₂.9 (n--C₄H₉)₁₂.1 and an organometal concentration of 1.20 mol/l.

(II) Synthesis of a solid material by the reaction with a chlorosilanecompound

To a 2-liter flask fitted with a dropping funnel and a cooler, havingbeen fully purged with nitrogen, there was charged one liter of hexanecontaining 1 mol of monomethyl dichlorosilane (HSiCl₂ CH₃) under astream of nitrogen. While the flask was maintained at 65° C., 500 mmolof the above-mentioned solution of an organomagnesium complex was addeddropwise over one hour through the dropping funnel. Thereafter, themixture was reacted with stirring at 65° C. for one hour. A white solidmaterial thus formed was filtered off, washed with n-hexane and dried toobtain 42.6 g of a white solid (A-2). Analysis of this solid showed thatit contained 9.18 mmol Mg, 19.20 mmol Cl, 1.70 mmol Si, and 0.60 mmolalkyl groups per gram of solid. The specific surface area measured bythe B.E.T. method was 216 m² /g.

(III) Synthesis of a solid catalyst component

To a 2 l vessel fully purged with nitrogen, the above white solid (A-2,20 g) and 600 ml of n-hexane were added with stirring. Then, 100 ml ofn-hexane and 15.0 mmol of 2-thiophenecarboxylic acid ethyl ester wereadded dropwise with stirring over one hour at 80° C. The mixture wasfurther reacted with stirring one hour at 65° C. The formed white solidwas filtered, washed with hexane, and dried to obtain a white solidmaterial (B-2).

To an autoclave having been purged with nitrogen were added 18 g of saidwhite solid material (B-2), and 300 ml of titanium tetrachloride. Themixture was reacted with stirring at 130° C. for 2 hours. The solidportion was filtered off, isolated, washed fully with hexane, and driedto obtain a solid (C-2).

The solid (C-2, 4.0 g) were fed under nitrogen atmosphere to a 100 mmstainless steel ball mill containing twenty five 9-mmφ stainless steelballs. The ball mill was vibrated at a speed of more than 1,000 vib/minfor 5 hours, to obtain a solid catalyst component (S-2). This componenthad a Ti content of 2.2 wt.%.

(IV) Slurry polymerization of propylene

The slurry polymerization of propylene was carried out in the samemanner as in Example 1, using the solid catalyst component (S-2, 50 mg)synthesized in (III), above, 2.4 mmol of triethylaluminum and 0.8 mmolof 2-thiophenecarboxylic acid ethyl ester. There were obtained 151 g ofhexane-insoluble polymer and 5.7 g of a hexane-soluble portion. Afterthe hexane-insoluble polymer was extracted with n-heptane, the remainingportion was 95.0%. The catalyst yield was 13,700 g of PP/g ofTi.hour.propylene pressure.

EXAMPLE 3

To an autoclave having been purged with nitrogen were fed 2.0 g of thesolid catalyst component (S-2) prepared in Example 2 and 30 ml oftitanium tetrachloride. The mixture was reacted with stirring at 130° C.for 2 hours. The solid portion was separated by filtration, washed fullywith hexane, and dried to obtain a solid catalyst component (S-3).Analysis of this solid showed that it contained 2.3% by weight oftitanium.

The slurry polymerization of propylene was conducted in the same manneras in Example 1, using the solid catalyst component (S-3, 30 mg), 2.4mmol of triethylaluminum and 0.8 mmol of 2-thiophenecarboxylic acidethyl ester. There were obtained 145 g of a hexane-insoluble polymer and4.4 g of a hexane-soluble portion. The catalyst yield was 21,000 g-PP/gof Ti.hour.propylene pressure. After the hexane-insoluble polymer wasextracted with n-heptane, the remaining portion was 96.4%.

EXAMPLE 4

Liquid propylene (350 g) was charged into a 1.5-liter autoclave, theinside of which had been purged with nitrogen and deaerated in vacuo.The inside temperature was raised to 60° C. The solid catalyst component(S-3, 10 mg) synthesized in Example 3, 1.8 mmol of triethylaluminum and0.6 mmol of 2-thiophenecarboxylic acid ethyl ester were then added tothe autoclave. While maintaining the inside temperature at 60° C., thepolymerization was allowed to proceed for 2 hours, to obtain 152 g of apolymer. The catalyst yield was 330,000 g of PP/g of Ti.hour. After thepolymer was extracted with n-heptane, the remaining portion was 94.6%.

COMPARATIVE EXAMPLE 1

A solid catalyst component was prepared in the same manner as in part(III), Example 1, using commercially available anhydrous magnesiumchloride instead of the solid material prepared in part (II), Example 1by reacting an organomagnesium complex with a chlorosilane compound. Thesolid catalyst component contained 0.81 wt.% of titanium. Slurrypolymerization was carried out in the same manner as in Example 1, using100 mg of this solid catalyst component, 2.4 mmol of triethylaluminum,and 0.8 mmol of 2-thiophenecarboxylic acid ethyl ester. There wereobtained 7.8 g of a hexane-insoluble polymer and 2.1 g of ahexane-soluble portion. After the hexane-insoluble polymer was extractedwith boiling n-heptane, the remaining portion was 77.2%. The catalystyield was 962 g of PP/g of Ti.hour.propylene pressure.

COMPARATIVE EXAMPLE 2

In the reaction of an organomagnesium complex with chlorosilanedescribed in part (II), Example 1, there was used methyltrichlorosilane, SiCl₃ CH₃, instead of HSiCl₃. 2.06 g of a white solidmaterial was obtained. Yield of the solid material was 1/20 that in part(II), Example 1.

EXAMPLE 5

A magnesium-containing solid (5.0 g) synthesized as in part (II),Example 1 and 40 mmol of 2-furan-carboxylic acid ethyl ester werereacted in the same manner as in Example 1. 4.5 g of the obtained solidand 0.38 g of titanium trichloride (TiCl₃.1/3AlCl₃ of a AA grade,prepared by Toyo Stauffer Company) were ground under nitrogen atmospherein a vibrating ball mill for 5 hours. This solid (C-5, 4.3 g) wasreacted with 60 ml of titanium tetrachloride at 130° C. for 2 hours withstirring. Thereafter the solid portion was filtered off, washed anddried to obtain a solid catalyst component (S-5). The solid catalystcomponent had a Ti content of 2.2 wt.%.

Slurry polymerization of propylene was conducted in the same mannerdescribed in Example 1, using 50 mg of the solid catalyst component(S-5), 2.4 mmol of triethylaluminum and 0.8 mol of 2-furancarboxylicacid ethyl ester. Results obtained were as given in Table 1.

EXAMPLE 6

Slurry polymerization of propylene was carried out in the same mannerdescribed in Example 5 except that 100 mg of the solid (C-5), wherein aTi-content was 1.7 wt.%, was used as the solid catalyst component.Results were as given in Table 1.

EXAMPLE 7

As the same manner described in Example 1, the magnesium-containingsolid was first reacted with 2-thiophenecarboxylic acid butyl ester,further reacted with titanium tetrachloride. 3.95 g of the obtainedsolid and 0.16 g of titanium trichloride (Grade AA, prepared by ToyoStauffer Company) were ground for 5 hours in a vibration type ball mill.The obtained solid (C-7, 3.2 g) was reacted with 80 ml of titaniumtetrachloride at 130° C. for 2 hours with stirring. After the reaction,a solid portion was filtered, washed and dried to obtain a solidcatalyst component (S-7) which had a Ti-content of 4.1 wt.%.

Slurry polymerization of propylene was carried out in the same manner asin Example 1, using 30 mg of the solid catalyst component (S-7), 2.4mmol of triethylaluminum and 0.8 mmol of 2-thiophenecarboxylic acidmethyl ester. Results are given in Table 1.

EXAMPLE 8

Slurry polymerization of propylene was conducted in the same mannerdescribed in Example 7 except that 50 mg of the solid (C-7), wherein aTi-content was 3.6 wt.%, was used as the solid catalyst component.Results are given in Table 1.

EXAMPLE 9 (I) Synthesis of a hydrocarbon-soluble organomagnesiumconjugated-complex

Di-n-butyl-magnesium (138 g), and triethylaluminum (19 g) together with1 l of heptane were introduced in a 2 l flask having been purged withnitrogen and the mixture was reacted at 80° C. for 2 hours, to obtain asolution of an organomagnesium complex. Analysis of this complex showedthat its composition was AlMg₆.0 (C₂ H₅)₂.9 (n--C₄ H₉)₁₂.1. It had anorganometal concentration of 1.15 mol/l.

In a vessel purged with nitrogen, 500 mmol of the above complex wasweighed, and 80 mmol of toluene solution of m-cresol (0.51 mol/l) wasadded dropwise with stirring over one hour to the vessel maintained at30° C. After the reaction, an organomagnesium conjugated complex wasobtained.

(II) to (IV) Synthesis of a solid material and a solid catalystcomponent; and polymerization

In the same manner described in part (II) of Example 1, a magnesiumcontaining solid was synthesized using 500 mmol of the above magnesiumconjugated complex and 500 mmol of dichloromethylsilane (HSiCl₂ CH₃)instead of trichlorosilane. Using the magnesium containing solid with2-thiophenecarboxylic acid methyl ester, a solid catalyst component wassynthesized in the same manner as in Example 3.

Slurry polymerization of propylene was conducted in the same manner asin Example 1, using 30 mg of the solid catalyst component, wherein thecontent was Ti 2.2 wt.%, 2.4 mmol of triethylaluminum and 0.8 mmol ofpyrrol-2-carboxylic acid ethyl ether. Results were as given in Table 1.

                  TABLE 1                                                         ______________________________________                                                                           Remaining                                                                     portion after                                                                 the hexane-                                       Hexane-   Hexane-   Cat. yield                                                                            insoluble                                         insoluble soluble   (g-PP/g-                                                                              polymer was                                       portion   portion   Ti · hour ·                                                         extracted with                                    of polymer                                                                              of polymer                                                                              propylene                                                                             boiling heptane                            Example                                                                              (g)       (g)       pressure)                                                                             (%)                                        ______________________________________                                        5      140       3.0       12700   95.7                                       6      132       5.2        8250   94.4                                       7      143       4.5       11600   96.5                                       8      156       6.0        8670   95.6                                       9      145       4.7       22000   96.7                                       ______________________________________                                    

EXAMPLES 10 TO 12 AND COMPARATIVE EXAMPLE 3

An organomagnesium conjugated complex was prepared by employing the sameprocedure described in Example 9 except that diethylketone was usedinstead of m-cresol. To obtain a magnesium containing solid, the sameprocedure as in Example 9 was repeated except that 1.0 mol oftrichlorosilane (HSiCl₃) and 500 mmol of the above organomagnesiumconjugated complex were used instead of 500 mmol of HSiCl₂ CH₃ and theorganomagnesium conjugated complex in Example 9, respectively. A solidcatalyst component was synthesized in the same manner as in Example 3,except for using the above magnesium containing solid and ethyl benzoate(instead of 2-thiophenecarboxylic acid methyl ester).

Polymerization of propylene was carried out in the same manner as inExample 1, using 30 mg of the solid catalyst component, (Ti content is2.3 wt.%), 2.4 mmol of triethylaluminum and the amount shown in Table 2of pyridine-3-carboxylic acid methyl ester. Results were as given inTable 2.

                                      TABLE 2                                     __________________________________________________________________________                   Results of polymerization                                             Amount of                   Remaining portion                                 pyridine-3-                                                                           Hexane-                                                                            Hexane-                                                                            Cat. yield                                                                              after the hexane-                                 carboxylic acid                                                                       insoluble                                                                          soluble                                                                            (g-PP/g-Ti · hour ·                                                   insoluble polymer was                             methyl ester                                                                          portion                                                                            portion                                                                            propylene extracted with heptane                            (mmol)  (g)  (g)  pressure) (%)                                        __________________________________________________________________________    Comparative                                                                   Example 3                                                                            0       136  9.5  19700     86.7                                       Example 10                                                                           0.3     163  10.8 23600     90.3                                       Example 11                                                                           0.6     153  5.8  22200     93.6                                       Example 12                                                                           0.8     141  3.1  20400     95.7                                       __________________________________________________________________________

EXAMPLES 13 TO 23

In the synthesis of a solid catalyst component in Example 2, componentsshown in Table 3 were used, and further treated with titaniumtetrachloride under the same procedure as in Example 3. Slurrypolymerization of propylene was carried out in the same manner describedin Example 3, using 30 mg of the treated solid catalyst component, 2.4mmol of an aluminum compound and 0.8 mmol of an electron donor shown inTable 3, respectively. The results obtained were as given in Table 3.

                                      TABLE 3                                     __________________________________________________________________________    Synthesis of solid catalyst component                                         __________________________________________________________________________    Synthesis of magnesium containing solid (1)                                                              Reaction                                                                      temperature(° C.)                                        Reaction-     ×            Ti-Compound (2)                    Organomagnesium                                                                         ratio                                                                              Chlorosilane                                                                           Reaction Carboxylic acid                                                                         grinding-time is                Ex.                                                                              component Mg/Si                                                                              compound time (hr.)                                                                             ester (3) shown by [hr.]                  __________________________________________________________________________    13 AlMg.sub.6.0 Et.sub.2.9 n-Bu.sub.12.1                                                   1/3  HSiCl.sub.2 C.sub.2 H.sub.5                                                            65° C. × 2 hrs.                                                           ethyl p-toluate                                                                         Ti(On-Bu).sub.3 Cl [5]          14 AlMg.sub.3.0 Et.sub.2.8 n-Bu.sub.6.2                                                    1/1  HSiCl.sub.2 CH.sub.3                                                                   "        ethyl p-anisate                                                                         Ti(Oi-Pr).sub.2 Cl.sub.2                                                      [5]                             15 ZnMg.sub.2.0 Et.sub.2.1 n-Bu.sub.3.9                                                    1/2  HSiCl.sub.3                                                                            "        methyl benzoate                                                                         Ti(On-Bu)Cl.sub.3 [10]          16 BeMg.sub.4.0 Et.sub.3.7 n-Pr.sub.6.3                                                    1/2  HSiCl.sub.2 C.sub.2 H.sub.5                                                            "        methyl 2-furan                                                                          TiCl.sub.4 [24]                                                     carboxylate                               17 BMg.sub.1.0 Et.sub.2.8 n-Pr.sub.2.2                                                     1/2  HSiClCH.sub.3 . C.sub.2 H.sub.5                                                        "        n-propyl benzoate                                                                       "                               18 sec-Bu.sub.2 Mg                                                                         1/2  HSiCl.sub.2 CH.sub.3                                                                   50° × 2 hrs.                                                              ethyl benzoate                                                                          "                               19 sec-BuMgEt                                                                              1/2  HSiCl(CH.sub.3).sub.2                                                                  "        methyl p-toluate                                                                        "                               20 (n-C.sub.6 H.sub.13).sub.2 Mg                                                           1/1  HSiCl.sub.2 C.sub.2 H.sub.5                                                            "        N-carboethoxy                                                                           "                                                                   pyrrol                                    21 n-BuMgCl . nBu.sub.2 O                                                                  1/2  HSiCl.sub.3                                                                            65° C. × 2 hrs.                                                           ethyl 2-thiophene                                                                       "                                                                   carboxylate                               22 n-BuMgCl  1/1  HSiCl.sub.2 CH.sub.3                                                                   "        ethyl pyridine-3-                                                                       "                                  (n-Bu.sub.2 O solution)          carboxylate                               23 n-BuMgCl  2/1  HSiCl.sub.3                                                                            "        Propyl 2-thiophene                                                                      "                                  (solid)                          carboxylate                               __________________________________________________________________________                     Polymerization results                                       1                        Yield of            Remaining portion                                 Ti-content                                                                            hexane-                                                                            Hexane-                                                                            Cat. yield                                                                              after the hexane-                Aluminum compound and electron                                                                 in solid                                                                              insoluble                                                                          soluble                                                                            (g-PP/g-Ti · hour                                                              insoluble polymer                donor (amount employed is                                                                      cat. component                                                                        polymer                                                                            portion                                                                            propylene was extracted with               the same as in Example 3)                                                                      (wt.%)  (g)  (g)  pressure) heptane (%)                      __________________________________________________________________________    Al(Et).sub.3                                                                        3-thiophene carboxylic                                                                   2.7     116  4.7  14300     93.3                                   acid ethyl ester                                                        "     2-furan carboxylic                                                                       2.6     129  5.3  16500     93.7                                   acid methyl ester                                                       "     coumalic acid ethyl                                                                      2.2     127  6.1  19200     94.3                                   ester                                                                   Al(i-Bu).sub.3                                                                      pyridine-4-carboxylic                                                                    2.1     136  4.3  21600     94.8                                   acid ethyl ester                                                        AlEt.sub.2. H                                                                       pyridine-2-carboxylic                                                                    2.3     126  5.0  18300     95.5                                   acid methyl ester                                                       AlEt.sub.3                                                                          pyrrol-2-carboxylic                                                                      2.7     138  5.3  17000     96.1                                   acid methyl ester                                                       "     pyridine-2-carboxylic                                                                    2.4     140  3.5  19400     93.9                                   acid ethyl ester                                                        "     2-thiophene carboxylic                                                                   2.5     145  4.3  19300     94.8                                   acid n-propyl ester                                                     "     2-thiophene carboxylic                                                                   2.8     136  3.4  16200     94.9                                   acid n-butyl ester                                                      "     N-carboethoxy pyrrol                                                                     3.5     140  3.9  13300     95.2                             "     2-furan carboxylic                                                                       2.6     115  4.1  12800     94.7                                   acid ethyl ester                                                        __________________________________________________________________________

EXAMPLE 24

In this example, the catalyst comprises 1.8 mmol of triethylaluminum,0.6 mmol of 2-thiophenecarboxylic acid ethyl ester and 10 mg of a solidcatalyst component having 2.4% of Ti obtained by the same proceduredescribed in Example 3. Using this catalyst, slurry polymerization wascarried out in the same procedure described in Example 1 except thatpropylene and hydrogen were charged at a pressure of 10 kg/cm² and at apartial pressure of 0.04 kg/cm², respectively, so as to keep a totalgauge pressure of 9.8 kg/cm². There were obtained 122 g of ahexane-insoluble polymer and 4.3 g of a hexane-soluble portion. Afterthe n-hexane-insoluble polymer was extracted with n-heptane, theremaining portion was 96.4%. The catalyst yield was 254000g-PP/g-Ti.hour.propylene pressure. The Ti-content and chlorine-contentin the hexane-insoluble polymer were 2 ppm and 55 ppm, respectively.Further the hexane-insoluble polymer showed 8.1 g/minute of MFI, bulkdensity of 0.43 g/cm³, 33.2° angle of repose and 91.5% particles of 35to 150 mesh.

EXAMPLE 25

Using a catalyst comprising 200 mg of the solid catalyst component (S-3)obtained in Example 3, 4.6 mmol of triethylaluminum and 1.2 mmol of2-thiophene carboxylic acid ethyl ester, polymerization of butene-1 wascarried out according to the polymerization conditions described inExample 1. There were obtained 50 g of a white polymer.

EXAMPLE 26

Using a catalyst comprising 200 mg of the solid catalyst component (S-3)obtained in Example 3, 4.6 mmol of triethyl aluminum and 1.2 mmol of2-thiophene carboxylic acid ethyl ester, polymerization of4-methylpentene-1 was carried out according to the polymerizationconditions described in Example 1. There were obtained 46 g of a whitepolymer.

EXAMPLE 27

Polymerization was carried out using 30 mg of the solid catalystcomponent (S-3) synthesized in Example 3, 2.4 mmol of triethylaluminumand 0.8 mmol of 2-thiophene carboxylic acid ethyl ester, and followingthe same procedure described in Example 1, except that apropylene-ethylene gas mixture containing 2 mol% of ethylene was used inplace of propylene. There were obtained 143 g of a white polymer.

EXAMPLE 28

The solid catalyst component (60 mg) synthesized in Example 3, 1.0 mmolof triisobutylaluminum, 0.1 mmol of 2-thiophenecarboxylic acid ethylester and 0.8 l of dehydrated and deaerated n-hexane were charged into a1.5 l autoclave, the inside of which had been fully purged with nitrogenand dried in vacuo. Then, the autoclave was maintained at 80° C. and wascharged with 1.6 kg/cm² of hydrogen followed by ethylene in order to get4.0 kg/cm² of total pressure. Polymerization was carried out for 1 hourby supplying ethylene so as to keep a total gauge pressure of 4.0kg/cm². There were obtained 144 g of a white polymer.

We claim:
 1. In a catalyst useful for polymerizing olefins comprising amagnesium compound, a titanium compound, an electron donor, and anorganometallic compound, wherein a solid (1) obtained by reacting onemole of (i) an organomagnesium component of the formula

    M.sub.α Mg.sub.β R.sub.p.sup.1 R.sub.q.sup.2 X.sub.r

wherein α, p, q and r each independently ≧0, β>0, p+q+r=mα+2β M is Al,Zn, B or Be, m is the valence of M, R¹ and R² are the same or differenthydrocarbon groups having 1-20 carbon atoms, and X is a halogen atom,orof the reaction product of M₆₀ Mg₆₂ R_(p) ¹ R_(q) ² X_(r) with anelectron donor, with 0.01 to 100 moles of (ii) a chlorosilane compoundcontaining Si--H bonds and of the formula

    H.sub.a SiClR.sub.4-(a+b).sup.3

wherein 0<a≦2, b>0, a+b≦4, and R³ is a hydrocarbon group having 1-20carbon atoms, is used as a catalyst raw material, a solid catalystcomponent (A) is obtained by reacting and/or grinding said solid (1), atitanium compound (2) selected from a tetravalent titanium compoundcontaining at least one halogen atom and/or a halide of trivalenttitanium, and a carboxylic acid ester (3) and said catalyst component(A) is used with a component (B) which is an organometallic compound anda carboxylic acid ester (3), the improvement wherein said last-mentionedcarboxylic acid ester (3) of component (B) is a nitrogen-, sulfur-and/or oxygen-containing heterocyclic carboxylic acid ester.
 2. Acatalyst for polymerizing olefins according to claim 1, wherein (3) of(B) is a lower alkyl ester of a nitrogen-containing heterocycliccarboxylic acid.
 3. A catalyst for polymerizing olefins according toclaim 1, wherein (3) of (B) is a lower alkyl ester of asulfur-containing heterocyclic carboxylic acid.
 4. A catalyst forpolymerizing olefins according to claim 1, wherein (3) of (B) is a loweralkyl ester of an oxygen-containing heterocyclic carboxylic acid.
 5. Acatalyst for polymerizing olefins according to claim 1, wherein solidcatalyst component (A) is further treated with a halide of tetravalenttitanium before combination with (B).
 6. A catalyst for polymerizingolefins according to claim 5, wherein the further treating tetravalenttitanium halide is titanium tetrachloride.
 7. A catalyst forpolymerizing olefins according to claim 1, wherein the organomagnesiumcomponent (i) is a hydrocarbon-soluble organomagnesium complex whichcorresponds to α>0 and r=0.
 8. A catalyst for polymerizing olefinsaccording to claim 1, wherein the organomagnesium component (i) is ahydrocarbon-soluble organomagnesium compound wherein α=0, r=0, and(a) R¹is a secondary or tertiary alkyl group having 4 to 6 carbon atoms, andR²is a hydrocarbon group having 4 to 6 carbon atoms, or (b) R¹ is an alkylgroup having 2 to 3 carbon atoms, andR² is an alkyl group having atleast 4 carbon atoms, or (c) R¹ and R² both are alkyl groups having atleast 6 carbon atoms.
 9. A catalyst for polymerizing olefins accordingto claim 1, wherein the organomagnesium component (i) is anorganomagnesium halide wherein α=0, β=1, q=0 and r=1.
 10. A catalyst forpolymerizing olefins according to claim 1, wherein α>0 and β/α is fromabout 0.5 to
 10. 11. A catalyst for polymerizing olefins according toclaim 1, wherein carboxylic acid ester (3) of component (A) is reactedwith the solid (1) in an amount of 0.001 to 50 mols per 1 mol ofhydrocarbon group remaining in solid (1).
 12. A catalyst forpolymerizing olefins according to claim 1, wherein the organometalliccompound of component (B) is an organoaluminum compound represented bythe general formula AlR_(n) ⁴ Z_(3-n), wherein R⁴ is a hydrocarbon grouphaving 1 to 20 carbon atoms; Z is hydrogen, halogen or an alkoxy,aryloxy or siloxy group; and n is 2 or 3.